Einführung von Substituenten in den 7‐Ring des Azulens mit Hilfe metallorganischer Verbindungen

Häfner, Klaus; Weldes, Helmut H.

doi:10.1002/ange.19550671106

Cited by 11 publications

(3 citation statements)

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“…7–10 for some of the history and literature). Hafner’s synthesis11, 12 has made the compound widely accessible. Its exceptional photophysics with fluorescence from the second excited singlet state S 2 violating Kasha’s rule was studied by Beer and Longuet Higgins13 and its intramolecular dynamics including isomerisation to naphthalene after electronic (UV/Vis) excitation has been studied in molecular beams,14, 15 shock waves16 and by femtosecond pump‐probe techniques 17.…”

Section: Character Table For the C2v And Ms4 Symmetry Groups Of Azulementioning

confidence: 99%

Synchrotron‐Based Rotationally Resolved High‐Resolution FTIR Spectroscopy of Azulene and the Unidentified Infrared Bands of Astronomy

2013

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Chasing the unidentified IR bands: The first rotationally resolved high-resolution infrared spectrum of azulene is reported using synchrotron Fourier transform infrared spectroscopy including a rovibrational analysis of the out-of-plane fundamental ν44. Comparison of azulene, naphthalene, indole, and biphenyl infrared bands leads to coincidences with UIR bands at 12.8 μm with naphthalene and at 13.55 and 14.6 μm with biphenyl bands, but excluding azulene as a strong absorber.

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Section: Character Table For the C2v And Ms4 Symmetry Groups Of Azulementioning

confidence: 99%

Synchrotron‐Based Rotationally Resolved High‐Resolution FTIR Spectroscopy of Azulene and the Unidentified Infrared Bands of Astronomy

2013

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“…In exploring the great reactivity of such novel RLi reagents Ziegler's principal finding was the generality of the carbolithiation by RLi of carbon−carbon double bonds, ranging from the highly conjugated, such as in 1,1-diphenylethylene ( 24 ), fulvenes, or azulenes (eq 22), − to the isolated olefinic linkage of ethylene (eq 23) to generate oligomer 25 . Further noteworthy was the finding that the carbolithiation of eq 22 is markedly accelerated in diethyl ether over its rate in benzene: the reaction in benzene requires several days for completion, the reaction in ether, minutes.…”

Section: The Era Of the Organolithium Reagent 1930−2000mentioning

confidence: 99%

Henry Gilman: American Pioneer in the Rise of Organometallic Chemistry in Modern Science and Technology

Eisch

2002

Organometallics

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The growth and development of organometallic chemistry from an esoteric, well-nigh alchemical art into a completely integrated and essential part of both current organic chemistry and inorganic chemistry have occurred with escalating rapidity over the last 150 years. The sesquicentennial history of organometallic chemistry falls rather naturally into three 50-year periods, each of which began with far-reaching discoveries: (1) the discovery of zinc alkyls by Frankland in 1849 and the use of such alkyls to prepare alkyls of other metals; (2) the discovery of organomagnesium halides by Grignard in 1900 and their many reactions with organic compounds; and (3) the dual discoveries of the existence and structure of ferrocene by Pauson and Miller in 1951 and of the polymerization of olefins by Ziegler and Natta in 1952-1953. The marked burgeoning of organometallic chemistry after World War I is traced to an international group of young pioneers launching their careers with high hope and vigor: Gilman, Kharasch, Ziegler, Wittig, Kipping, Pope, Grignard and his school, Nesmeyanov, and Razuvaev. The thesis of this historical review is that Henry Gilman, through the breadth and depth of his numerous, original contributions on covalent, σ-bonded organometallics, is the one pioneer of this group who has integrated and systematized the great lode of empirical observations on organometallics into correlations with the metal's position in a Mendeleevian periodic table. He has thereby transformed this field from alchemical art into chemical science. In support of this thesis of Henry Gilman as the prototypical pioneer of modern organometallic chemistry, this account traces his academic career at Iowa State and points out his scientific contributions made at successive stages: (1) his studies of the Grignard reagents, which did much to make their preparation convenient and reliable and their reactions of broad and useful scope; (2) his investigations of organolithium reagents and his discovery and key development of the lithium-hydrogen and lithium-halogen exchange processes, which reactions were studied independently by Karl Ziegler and by Georg Wittig but merit being termed the Gilman lithium-hydrogen exchange and the Gilman-Wittig lithium-halogen exchange reactions, respectively; (3) the preparation and reactions of many other organometallics, obtained by the transmetalation reaction of the appropriate metal salts with a magnesium or lithium organometallic; and (4) finally the preparation, structure, and chemical reactivity of diverse organometallics of group 14, especially those with metal-metal and metal-alkali metal bonds. It can be argued with great cogency that such a lifetime of research set the stage and drew the curtail for the dawn of the third era of organometallic chemistry: the discovery and utility of π-bonded organometallics. Because of Gilman's towering role in uncovering, developing, and systematizing the chemistry of σ-bonded organometallics, many of Gilman's colleagues and former students had thought him dese...

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“…But it is interesting to note that in azulene there is an unmistakable tendency for each ring, the five-membered one as well as the seven-membered one, to possess a sextet of Tr-electrons, two Tr-electrons again being shared. This tendency finds expression in the dipole moment of azulene (9) and in the fact that electrophilic attack occurs on the five-membered ring (10)(11)(12)(13)(14)(15) and nucleophilic attack on the seven-membered ring (16). One may therefore write (VI) as an extreme structure for azulene.…”

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confidence: 99%

Representation of polycyclic aromatic compounds

Bieber¹

1958

J. Chem. Educ.

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Einführung von Substituenten in den 7‐Ring des Azulens mit Hilfe metallorganischer Verbindungen

Cited by 11 publications

References 2 publications

Synchrotron‐Based Rotationally Resolved High‐Resolution FTIR Spectroscopy of Azulene and the Unidentified Infrared Bands of Astronomy

Synchrotron‐Based Rotationally Resolved High‐Resolution FTIR Spectroscopy of Azulene and the Unidentified Infrared Bands of Astronomy

Henry Gilman: American Pioneer in the Rise of Organometallic Chemistry in Modern Science and Technology

Representation of polycyclic aromatic compounds

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